TWI743380B - Thermoplastic resin composition for plating, resin molded article and plated processed article - Google Patents

Abstract

The present invention provides a thermoplastic resin composition for plating which is capable of exerting an excellent plating adhesion strength even at high speed molding, suppressing a change of the plating appearance in a cold / heat cycle, obtaining a resin molded product excellent in impact resistance, and obtaining an excellent flowability during the molding process; and also provides a resin molded articles and a plated product using the thermoplastic resin composition. The thermoplastic resin composition includes predetermined amounts of (A) a rubber-containing graft copolymer mixture comprising two or more kinds of rubber-containing graft copolymers obtained by copolymerizing a predetermined monomer mixture in the presence of a diene rubber polymer and a hard copolymer (B). The graft copolymer mixture (A) has a rubber-containing graft copolymer (A-1) and a rubber-containing graft copolymer (A-II), wherein the rubber-containing graft copolymer (A-1) contains a mass average particle diameter of the rubbery polymer contained is 15 μm or more and less than 0.25 μm, and a proportion of particles having a particle diameter of more than 0.122 μm and 0.243 μm or less in the entire particles of the rubber-containing graft copolymer (A-1) is in the specific range; and the rubber-containing graft copolymer (A-II) has a mass average particle diameter of the rubbery polymer is 0.25μm or more and 0.5 μm or less.

Description

Thermoplastic resin composition for plating, resin molded products, and plated processed products

The present invention relates to a thermoplastic resin composition for plating, a resin molded product, and a plated processed product.

This application claims priority based on Japanese Patent Application No. 2017-141655 filed in Japan on July 21, 2017, and the content of this application is incorporated herein.

Molded products made of ABS (Acrylonitrile Butadiene Styrene) resin are used in OA (Office Automation) equipment because of their excellent impact resistance, mechanical strength, and chemical resistance. , Information equipment, communication equipment, electronic equipment, electrical equipment, home appliances, automobiles, construction and other wide fields. In addition, the molded article made of ABS resin has the characteristics of excellent plating appearance, high adhesion strength of the plating film, and excellent cooling and heating cycle characteristics when plating processed products are made, so it is used in plastic plating. It is also used for various purposes in covering purposes. For example, in the automotive field, it seeks to expand the plating application for radiator parts or emblem parts.

The plating characteristics are easily affected by the characteristics of the resin composition forming the molded product or the factors of the molding conditions. Therefore, when a resin composition containing ABS resin is used, poor appearance of the plating may also occur. In the case of poor molding conditions, the plating film will have poor appearance such as peeling or swelling, which will significantly impair the commercial value of the final product.

Under such circumstances, as a thermoplastic resin composition that has high adhesion strength of the plated film and does not swell or crack in the plated film during cooling and heating cycles, it has been proposed to contain predetermined copolymers and adhesives in a predetermined ratio. A thermoplastic resin composition of a branch copolymer and an organosilicon compound (Patent Document 1).

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 8-193162.

In recent years, in response to increasing the efficiency of the production system in response to the reduction of various types of products, etc., production has been carried out under high-speed molding conditions in order to shorten the molding cycle of molded products.

However, when the thermoplastic resin composition of Patent Document 1 is molded under high-speed molding conditions, the obtained molded product cannot exhibit sufficient plating adhesion strength when plating is performed, and it is plated in a cold and heat cycle test. The film is prone to peeling or swelling. In addition, the impact resistance of the molded product and the fluidity during molding processing are not necessarily sufficient.

The object of the present invention is to provide a thermoplastic resin composition for plating, a resin molded product using the thermoplastic resin composition for plating, and a plated processed product. It can also exhibit excellent plating adhesion strength, the appearance of the plating is not easy to change during the cooling and heating cycle, the resin molded product with excellent impact resistance, and the fluidity during molding processing.

The present invention includes the following aspects.

[1] A thermoplastic resin composition for plating, comprising a rubber-containing graft copolymer mixture (A) and a rigid copolymer (B). The rubber-containing graft copolymer mixture (A) is composed of two or more It is composed of a rubber-containing graft copolymer. The aforementioned rubber-containing graft copolymer is copolymerized by copolymerizing a monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a diene rubber polymer. The aforementioned rigid copolymer (B) has a monomer unit derived from an aromatic vinyl compound and a monomer unit derived from a vinyl cyanide compound; the aforementioned rubber-containing graft copolymer mixture (A) contains a rubber-containing Graft copolymer (AI) and rubber-containing graft copolymer (A-II), the mass average particle size of the diene rubber polymer in the rubber-containing graft copolymer (AI) is 0.15 μm The proportion of particles above and less than 0.25μm with a particle size of more than 0.122μm and below 0.243μm in all the particles of the diene rubber polymer is 50% by mass or more. The rubber-containing graft copolymer The mass average particle diameter of the aforementioned diene rubber polymer in (A-II) is 0.25 μm or more and 0.5 μm or less; the content of the aforementioned rubber-containing graft copolymer (AI) is relative to the aforementioned rubber-containing graft copolymer The total mass of the mixture (A) is 60% by mass or more and less than 95% by mass; when the total mass of the rubber-containing graft copolymer mixture (A) and the rigid copolymer (B) is set to 100 parts by mass The content of the rubber-containing graft copolymer mixture (A) is 25 parts by mass or more and 50 parts by mass or less, and the content of the rigid copolymer (B) is 50 parts by mass or more and 75 parts by mass or less.

[2] The thermoplastic resin composition for plating according to [1], wherein the rigid copolymer (B) comprises a rigid copolymer (BI), and the mass average molecular weight of the rigid copolymer (BI) is 50,000 or more and 80,000 or less, and The content of the monomer unit derived from the vinyl cyanide compound is 30% by mass or more and 35% by mass or less with respect to the total mass of the aforementioned rigid copolymer.

[3] A resin molded product composed of the thermoplastic resin composition for plating as in [1] or [2].

[4] A plated processed product having a resin molded product and a plated film, the resin molded product is the resin molded product of [3], and the plated film is formed on at least a part of the surface of the resin molded product.

According to the present invention, it is possible to provide a thermoplastic resin composition for plating, a resin molded product using the thermoplastic resin composition for plating, and a plated processed product. The thermoplastic resin composition for plating can be obtained even during high-speed molding. It can exhibit excellent plating adhesion strength, the appearance of the plating is not easy to change during the cooling and heating cycle, the resin molded product with excellent impact resistance, and the fluidity during molding processing.

Hereinafter, the present invention will be explained in detail.

[Thermoplastic resin composition for plating]

The thermoplastic resin composition for plating of the present invention contains a rubber-containing graft copolymer mixture (A) and a rigid copolymer (B).

The thermoplastic resin composition for plating of the present invention may further contain other components other than the aforementioned rubber-containing graft copolymer mixture (A) and the rigid copolymer (B) as needed, within a range that does not impair the effects of the present invention.

<Graft copolymer mixture containing rubber (A)>

The rubber-containing graft copolymer mixture (A) is composed of two or more kinds of rubber-containing graft copolymers.

Two or more kinds of rubber-containing graft copolymers constituting the rubber-containing graft copolymer mixture (A) are each composed of an aromatic vinyl compound and a cyanide vinyl compound in the presence of a diene-based rubber polymer The monomer mixture is copolymerized to form a copolymer. That is, it is a copolymer containing a rigid copolymer component (A') obtained by graft-polymerizing a diene rubber polymer, an aromatic vinyl compound, and a vinyl cyanide compound. In addition to the rigid copolymer component (A'), the aforementioned rubber-containing graft copolymer may further include homopolymers of aromatic vinyl compounds, homopolymers of vinyl cyanide compounds, and aromatic vinyl compounds and Copolymer of cyanide vinyl compound.

The aforementioned monomer mixture may optionally further contain other copolymerizable compounds other than the aromatic vinyl compound and the vinyl cyanide compound. That is, the aforementioned rubber-containing graft copolymer may also be obtained by copolymerizing a diene-based rubber polymer, an aromatic vinyl compound, a vinyl cyanide compound, and other copolymerizable compounds as necessary. Copolymer.

The rubber-containing graft copolymer mixture (A) includes at least the rubber-containing graft copolymer (A-I) and the rubber-containing graft copolymer (A-II) as the rubber-containing graft copolymer.

The rubber-containing graft copolymer (AI) is a diene rubber polymer with a mass average particle size of 0.15μm or more and less than 0.25μm, and particles with a particle size of more than 0.122μm and 0.243μm or less. The rubber-containing graft copolymer in which the proportion of all particles of the rubber polymer is 50% by mass or more. The rubber-containing graft copolymer (A-II) is a rubber-containing graft copolymer with a diene rubber polymer with a mass average particle size of 0.25 μm or more and 0.5 μm or less.

The mass average particle diameter of the diene rubber polymer in the rubber-containing graft copolymer (A-I) is preferably 0.15 μm or more and less than 0.25 μm, more preferably 0.18 μm or more and less than 0.23 μm.

If the mass average particle diameter of the diene rubber polymer in the rubber-containing graft copolymer (AI) is within this range, the adhesion strength characteristics, thermal cycle characteristics, impact resistance, and Any one of liquidity decreases.

The mass average particle size is measured by the method described in the examples described later.

The proportion of particles with a particle size of more than 0.122 μm and less than 0.243 μm in the rubber-containing graft copolymer (AI) in the total particles of the diene-based rubber polymer is 50% by mass or more, preferably 60 Above mass%. If the proportion of the aforementioned particles in the rubber-containing graft copolymer (AI) is 50% by mass or more, it is possible to suppress any reduction in adhesion strength characteristics, thermal cycle characteristics, impact resistance, and fluidity in the plating step. . The upper limit of the ratio of the aforementioned particles is not particularly limited, and it may be 100% by mass.

The ratio of the aforementioned particles is determined based on the particle size distribution on a mass basis. The particle size distribution on a mass basis is measured by the method described in the below-mentioned Examples.

The mass average particle diameter of the diene rubber polymer in the rubber-containing graft copolymer (A-II) is 0.25 μm or more and 0.50 μm or less, preferably 0.30 μm or more and 0.40 μm or less. If the mass average particle diameter of the diene rubber polymer in the rubber-containing graft copolymer (A-II) is within this range, the adhesion strength characteristics, thermal cycle characteristics, and impact resistance in the plating step can be suppressed Decrease in either sex or liquidity.

The content of the rubber-containing graft copolymer (AI) in the rubber-containing graft copolymer mixture (A) is 60% by mass or more and less than 95% by mass relative to the total mass of the graft copolymer mixture (A), It is preferably 70% by mass or more and less than 90% by mass. If the content of the rubber-containing graft copolymer (A-I) is within this range, it is possible to suppress any decrease in adhesion strength characteristics, thermal cycle characteristics, impact resistance, and fluidity in the plating step.

The content of the rubber-containing graft copolymer (A-II) in the rubber-containing graft copolymer mixture (A) relative to the total mass of the graft copolymer mixture (A) is preferably more than 5% by mass and is 40% by mass or less, preferably more than 10% by mass and 30% by mass or less. If the content of the rubber-containing graft copolymer (A-II) is within this range, it is possible to suppress any reduction in adhesion strength characteristics, thermal cycle characteristics, impact resistance, and fluidity in the plating step.

As the raw material of rubber-containing graft copolymers (rubber-containing graft copolymers (AI), (A-II), etc.), diene rubber polymers include: polybutadiene, butadiene, and Copolymers of vinyl monomers copolymerized with butadiene (such as styrene-butadiene, acrylonitrile-butadiene, etc.), polyisoprene, etc. These diene-based rubber polymers may be used singly, or two or more of them may be used in combination. Among them, polybutadiene is preferred.

The diene rubber polymer may also be a swollen rubber obtained by swelling the aforementioned diene rubber polymer. In addition, the mass average particle size, distribution, etc. can be adjusted by the bulging operation. Examples of the swelling method include a mechanical coagulation method, a chemical coagulation method, and a coagulation method using an acid group-containing copolymer.

As a chemical coagulation method, the following method can be cited: adding an acidic substance to the diene rubber polymer latex to make the emulsion stability unstable and coagulate to reach the target particle size, adding an alkaline substance to polymerize the diene rubber The latex is then stabilized. Examples of acidic substances include acetic acid, acetic anhydride, sulfuric acid, phosphoric acid, and the like. Examples of alkaline substances include potassium hydroxide and sodium hydroxide.

As a coagulation method using the acid group-containing copolymer, the following method can be cited: mixing a diene-based rubber polymer latex with an acid group-containing copolymer latex to obtain a swollen rubber latex. As an acid group-containing copolymer latex, for example, a latex of an acid group-containing copolymer obtained by the following method: that is, in water, it contains an acid group-containing monomer (such as methacrylic acid, acrylic acid, etc.) Carboxyl group monomers), (meth)acrylic acid alkyl ester monomers, and if necessary, the monomer components of other monomers that can be copolymerized with the aforementioned acid group-containing monomers and (meth)acrylic acid alkyl ester monomers. polymerization.

Aromatic vinyl compounds as raw materials for rubber-containing graft copolymers include: styrene, α-methylstyrene, vinyl toluenes (p-methylstyrene, etc.), halogenated styrenes (p-bromobenzene, etc.) Ethylene, p-chlorostyrene, etc.), p-tert-butyl styrene, dimethyl styrene, vinyl naphthalene, etc. These aromatic vinyl compounds may be used individually by 1 type, and may use 2 or more types together. Among them, styrene and α-methylstyrene are preferred.

The vinyl cyanide compound used as the raw material of the rubber-containing graft copolymer includes acrylonitrile and methacrylonitrile. These vinyl cyanide compounds may be used individually by 1 type, and may use 2 or more types together. Among them, acrylonitrile is preferred.

Examples of other copolymerizable compounds that can be used as raw materials for rubber-containing graft copolymers include: methyl methacrylate, methyl acrylate and other methacrylic acid or acrylates; N-phenylmaleimide, N -Maleimide compounds such as cyclohexylmaleimide; unsaturated carboxylic acid compounds such as acrylic acid, methacrylic acid, itaconic acid, and fumaric acid. These compounds may be used individually by 1 type, and may use 2 or more types together.

The content of the diene-based rubber polymer-derived component in the rubber-containing graft copolymer relative to the total mass of the rubber-containing graft copolymer is preferably 30% by mass or more and 70% by mass or less, more preferably 40% by mass or more and 60% by mass or less. If the content of the component derived from the diene rubber polymer in the rubber-containing graft copolymer is within this range, the adhesion strength characteristics, thermal cycle characteristics, impact resistance, and fluidity in the plating step will be more excellent .

The content of the aromatic vinyl compound-derived component in the rubber-containing graft copolymer relative to the total mass of the rubber-containing graft copolymer is preferably 18% by mass or more and 60% by mass or less, more preferably 30% by mass % Above 50% by mass.

If the content of the aromatic vinyl compound-derived component in the rubber-containing graft copolymer is within the above range, the adhesion strength characteristics, thermal cycle characteristics, impact resistance, and fluidity in the plating step will be more excellent.

The content of the cyanide vinyl compound-derived component in the rubber-containing graft copolymer relative to the total mass of the rubber-containing graft copolymer is preferably 4% by mass or more and 25% by mass or less, more preferably 10% by mass % Or more and 20 mass% or less.

If the content of the component derived from the cyanide vinyl compound in the rubber-containing graft copolymer is within the above range, the adhesion strength characteristics, thermal cycle characteristics, impact resistance, and fluidity in the plating step will be more excellent.

The content of components derived from other copolymerizable compounds in the rubber-containing graft copolymer relative to the total mass of the rubber-containing graft copolymer is preferably 0 mass% or more and 15 mass% or less, more preferably 0 mass% % Or more and 10 mass% or less.

If the content of the components derived from other copolymerizable compounds in the rubber-containing graft copolymer is within the above range, the adhesion strength characteristics, thermal cycle characteristics, impact resistance, and fluidity in the plating step will be more excellent.

Each component of the two or more rubber-containing graft copolymers constituting the rubber-containing graft copolymer mixture (A) (components derived from diene-based rubber polymers, components derived from aromatic vinyl compounds) The types and contents of components, components derived from vinyl cyanide compounds, etc.) may be the same or different, respectively.

The rubber-containing graft copolymer is obtained by copolymerizing a monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a diene rubber polymer.

There are no particular limitations on the method of polymerization, but in terms of control so that the reaction can proceed stably, emulsion polymerization is preferred. Specifically, the following methods can be cited: the method of adding monomer mixture to the latex of the diene rubber polymer at one time and then polymerization; the method of adding a part of the monomer mixture to the latex of the diene rubber polymer first, In addition, the polymerization is carried out at any time while the remaining part is added to the polymerization system; the entire amount of the monomer mixture is added to the latex of the diene rubber polymer while the polymerization is carried out at any time; the aforementioned various methods can be used It is done in one stage or divided into two or more stages. When it is divided into two or more stages, it can also be carried out by changing the type or composition ratio of the monomers constituting the monomer mixture in each stage. The rubber-containing graft copolymer obtained by emulsion polymerization is usually in the state of latex.

Emulsion polymerization usually uses a radical polymerization initiator and emulsifier.

Examples of the radical polymerization initiator include peroxides, azo-based initiators, and redox-based initiators obtained by combining an oxidizing agent and a reducing agent. Among them, a redox initiator is preferred, and a hyposulfate based on a combination of ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, sodium formaldehyde sulfoxylate, and hydrogen peroxide is particularly preferred. Beginner.

The emulsifier is not particularly limited. In terms of the stability of the latex during radical polymerization and the improvement of the degree of polymerization, sodium sarcosine, potassium fatty acid, sodium fatty acid, dipotassium alkenyl succinate, and rosin acid soap are preferred. And other carboxylates. Among them, in terms of suppressing gas generation when the obtained rubber-containing graft copolymer and the thermoplastic resin composition containing the rubber-containing graft copolymer are subjected to high-temperature molding, the alkenyl amber is preferred Dipotassium acid. Specific examples of dipotassium alkenyl succinate include dipotassium octadecenyl succinate, dipotassium heptadecenyl succinate, and dipotassium hexadecenyl succinate. These emulsifiers may be used individually by 1 type, and may be used in combination of 2 or more types.

During the polymerization, in order to control the molecular weight or graft rate of the obtained rubber-containing graft copolymer, various well-known chain transfer agents may be added.

The polymerization conditions can be, for example, 30°C or more and 95°C or less, and 1 hour or more and 10 hours or less.

The rubber-containing graft copolymer is usually obtained in the state of latex. As a method of recovering the rubber-containing graft copolymer from the rubber-containing graft copolymer latex, for example, the following method can be cited: coagulation by throwing the graft copolymer latex into hot water in which a coagulant is dissolved The wet method of precipitation into a slurry, the spray drying method of semi-directly recovering the rubber-containing graft copolymer by spraying the latex of the rubber-containing graft copolymer into a heating atmosphere, etc.

Examples of the coagulant used in the wet process include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid; metal salts such as calcium chloride, calcium acetate, and aluminum sulfate, etc., which can be selected according to the emulsifier used in the polymerization. For example, when only carboxylic acid soaps such as fatty acid soaps or rosin acid soaps are used as emulsifiers, one or more of the above-mentioned coagulants can be used. When an emulsifier whose sodium alkylbenzene sulfonate is equal to the acidic region and also exhibits stable emulsifying power is used as the emulsifier, the coagulant is preferably a metal salt.

If the wet method is used, a slurry-like rubber-containing graft copolymer can be obtained. As a method of obtaining a rubber-containing graft copolymer in a dry state from the slurry-like rubber-containing graft copolymer, the following method can be cited: first, the remaining emulsifier residue is dissolved in water and washed, and then After the slurry is dewatered by a centrifugal or pressurized dewatering machine, etc., it is dried by an airflow dryer or the like; a dewatering and drying method is simultaneously performed by a press dewatering machine or an extruder, etc. By the above method, a dry rubber-containing graft copolymer in powder or particle form can be obtained.

The washing conditions are not particularly limited, but it is preferable to perform washing under the condition that the amount of emulsifier residue contained in 100% by mass of the rubber-containing graft copolymer after drying becomes 2% by mass or less.

Furthermore, the rubber-containing graft copolymer discharged from the press dehydrator or extruder may not be recovered, but may be directly sent to the extruder or molding machine for manufacturing the resin composition to form a molded product.

<Hard Copolymer (B)>

The rigid copolymer (B) is a copolymer having a monomer unit derived from an aromatic vinyl compound and a monomer unit derived from a vinyl cyanide compound. The rigid copolymer (B) may further have monomer units derived from other copolymerizable compounds other than the aromatic vinyl compound and the vinyl cyanide compound as needed.

The aromatic vinyl compound, vinyl cyanide compound, and other copolymerizable compounds used as necessary in the rigid copolymer (B) can be used with the above-mentioned rubber-containing graft copolymer mixture (A). Compounds with the same compound have the same preferred aspects.

The content of the aromatic vinyl compound-derived monomer unit in the rigid copolymer (B) is not particularly limited. For example, relative to the total mass of the rigid copolymer (B), it is preferably 50% by mass or more and 85% by mass or less , More preferably 60% by mass or more and 75% by mass or less.

If the content of the aromatic vinyl compound-derived monomer unit in the rigid copolymer (B) is in the above range, the adhesion strength characteristics, thermal cycle characteristics, impact resistance, and fluidity in the plating step will be more excellent.

The content of the monomer unit derived from the cyanide vinyl compound in the rigid copolymer (B) is not particularly limited. For example, relative to the total mass of the rigid copolymer (B), it is preferably 15% by mass or more and 50% by mass or less , More preferably 25% by mass or more and 40% by mass or less.

If the content of the monomer unit derived from the vinyl cyanide compound in the rigid copolymer (B) is in the above range, the adhesion strength characteristics, thermal cycle characteristics, impact resistance, and fluidity in the plating step are more excellent.

The mass average molecular weight of the rigid copolymer (B) can be, for example, 50,000 or more and 150,000 or less.

The mass average molecular weight of the rigid copolymer (B) is a value in terms of standard polystyrene measured using gel permeation chromatography (GPC; Gel Permeation Chromatography).

The rigid copolymer (B) preferably contains a rigid copolymer (BI), the rigid copolymer (BI) has a mass average molecular weight of 50,000 or more and 80,000 or less, and the content of monomer units derived from the cyanide vinyl compound is relative to the aforementioned The total mass of the rigid copolymer is 30% by mass or more and 35% by mass or less. If the rigid copolymer (B-I) is included, the adhesion strength characteristics, thermal cycle characteristics, impact resistance, and fluidity in the plating step are more excellent.

The mass average molecular weight of the rigid copolymer (B-I) is more preferably 60,000 or more and 80,000 or less. The content of the monomer unit derived from the vinyl cyanide compound is preferably 31% by mass or more and less than 34% by mass relative to the total mass of the rigid copolymer (B-I).

The content of the hard copolymer (B-I) in the hard copolymer (B) relative to the total mass of the hard copolymer (B) is preferably 20% by mass or more, more preferably 35% by mass or more. In terms of impact resistance, the upper limit of the content of the rigid copolymer (B-I) is preferably 90% by mass or less.

The rigid copolymer (B) (the rigid copolymer (B-I), etc.) can be produced by copolymerizing an aromatic vinyl compound, a vinyl cyanide compound, and other copolymerizable compounds as necessary.

As the polymerization method, any of known polymerization methods such as emulsion polymerization, suspension polymerization, bulk polymerization, or a method of combining these can be applied.

<Other ingredients>

Examples of other components include various additives and other resins.

Examples of additives include: well-known antioxidants, light stabilizers, ultraviolet absorbers, lubricants, plasticizers, stabilizers, transesterification reaction inhibitors, hydrolysis inhibitors, mold release agents, antistatic agents, colorants (pigment , Dyes, etc.), carbon fiber, glass fiber, wollastonite, calcium carbonate, silica, talc and other fillers, brominated flame retardants, phosphorus flame retardants and other flame retardants, antimony trioxide and other flame retardant additives , Fluorine resin and other anti-dripping agents, antibacterial agents, antifungal agents, silicone oils, coupling agents, etc. One of these additives may be used alone, or two or more of them may be used in combination.

Examples of other resins include HIPS (High Impact Polystyrene) resin, ABS resin, ASA (Acrylonitrile Styrene Acrylate; acrylonitrile-styrene-acrylate) resin, AES (Acrylonitrile Ethylene Styrene; acrylonitrile). -Ethylene-styrene) resin, SAS (Styrene Acrylonitrile Styrene; styrene-acrylonitrile-styrene) resin and other rubber-reinforced styrene resins, AS (Acrylonitrile Styrene; acrylonitrile-styrene) resin, polystyrene resin, Nylon resin, methacrylic resin, polyvinyl chloride resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polyphenylene ether resin, polycarbonate resin, etc. In addition, it may be a resin obtained by blending two or more kinds of these resins, or a resin obtained by modifying these resins with a compatibilizer, a functional group, or the like.

Furthermore, as an essential component or optional component used in the present invention, as long as there is no problem in quality, it is possible to use a product recovered from a polymerization step, a processing step, or a step at the time of molding, or a recycled product recovered from the market.

<Content of each ingredient>

In the thermoplastic resin composition for plating of the present invention, when the total mass of the rubber-containing graft copolymer mixture (A) and the rigid copolymer (B) is 100 parts by mass, the rubber-containing graft copolymer mixture ( The content of A) is 25 parts by mass or more and 50 parts by mass or less, the content of the rigid copolymer (B) is 50 parts by mass or more and 75 parts by mass or less, preferably the content of the rubber-containing graft copolymer mixture (A) is 35 Parts by mass or more and 45 parts by mass or less, and the content of the rigid copolymer (B) is 55 parts by mass or more and 65 parts by mass or less. If the content of the rubber-containing graft copolymer mixture (A) and the rigid copolymer (B) is within this range, the adhesion strength characteristics, thermal cycle characteristics, impact resistance, and fluidity in the plating step are excellent.

Regarding the content of other components in the thermoplastic resin composition for plating of the present invention, when the total mass of the rubber-containing graft copolymer mixture (A) and the rigid copolymer (B) is 100 parts by mass, it is preferably 0 part by mass or more and 250 parts by mass or less, more preferably 0 part by mass or more and 100 parts by mass or less.

<Manufacturing Method of Thermoplastic Resin Composition for Plating>

The thermoplastic resin composition for plating of the present invention is produced by mixing and kneading the rubber-containing graft copolymer mixture (A), the rigid copolymer (B), and other components used as needed. The method of mixing and kneading the components of the thermoplastic resin composition is not particularly limited, and any general mixing and kneading method can be used. Examples include: after kneading with an extruder, a Banbury mixer, a kneading roll, etc. A method of cutting and granulating with a granulator, etc.

The thermoplastic resin composition for plating of the present invention is molded into a resin molded product.

Regarding the thermoplastic resin composition for plating of the present invention, it contains a rubber-containing graft copolymer mixture (A) and a rigid copolymer (B), and the rubber-containing graft copolymer mixture (A) includes a rubber-containing graft copolymer (AI) and rubber-containing graft copolymer (A-II), the content of rubber-containing graft copolymer (AI) is 60% by mass or more and less than 95% by mass, and the rubber-containing graft copolymer When the total mass of the mixture (A) and the rigid copolymer (B) is set to 100 parts by mass, the content of the rubber-containing graft copolymer mixture (A) is 25 parts by mass or more and 50 parts by mass or less, and the rigid copolymer (B) With a content of 50 parts by mass or more and 75 parts by mass or less, it is possible to obtain a resin molded product that exhibits excellent plating adhesion strength even during high-speed molding, does not change the plating appearance easily during cold and heat cycles, and has excellent impact resistance. In addition, the fluidity during forming is also excellent.

[Resin molded products]

The resin molded product of the present invention is composed of the above-mentioned thermoplastic resin composition of the present invention.

The resin molded product of the present invention is obtained by molding the thermoplastic resin composition of the present invention.

The molding method of the thermoplastic resin composition of the present invention is not limited in any way. Examples of the molding method include an injection molding method, an extrusion molding method, a compression molding method, an insert molding method, a vacuum molding method, and a blow molding method.

Since the resin molded product of the present invention uses the thermoplastic resin composition for plating of the present invention, even in the case of high-speed molding, the plating process also exhibits excellent plating adhesion strength, and the plating appearance during cold and heat cycles It is not easy to change and has excellent impact resistance.

[Plating processed products]

The plated processed product of the present invention has the above-mentioned resin molded product of the present invention and a plating film formed on at least a part of the surface of the aforementioned resin molded product.

The plated processed product of the present invention is obtained by subjecting the resin molded product of the present invention to a plating process. The plating treatment method is not limited in any way. As the plating method, for example, an electroless plating method, a direct plating method, and a chromium-free plating method can be cited.

Since the plated processed product of the present invention uses the resin molded product of the present invention, the adhesion strength between the resin molded product and the plating film is excellent, the appearance of the plating is not easily changed during a cold and hot cycle, and the impact resistance is also excellent.

The plated processed product of the present invention can be preferably used for various applications including OA equipment, information equipment, communication equipment, electronic equipment, electrical equipment, household appliances, automobiles, and construction.

[Example]

Hereinafter, synthesis examples, examples, and comparative examples are given to explain the present invention more specifically, but the present invention is not limited by the following examples as long as it does not exceed the gist of the present invention.

In addition, the following "parts" means "parts by mass".

<Mass particle size distribution of rubber polymer>

For the water-diluted solution of rubber polymer latex, a nanoparticle particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., Nanotrac UPA-EX150) based on the principle of dynamic scattering theory is used to measure the particle size distribution on a mass basis. According to the obtained particle size distribution, find the mass average particle size (μm) and the proportion (mass%) of particles with a particle size exceeding 0.122μm and less than 0.243μm in all particles (hereinafter also referred to as "exceeding 0.122μm and the mass% of particles below 0.243μm").

<Composition ratio of rigid copolymer (B)>

The composition ratio of the rigid copolymer (B) is based on the residual monomer amount after the GC-2014 quantitative reaction of Shimadzu Corporation is used to calculate the fixed amount (the amount that is incorporated into the copolymer in the form of monomer units). ).

<Mass average molecular weight (Mw) of the rigid copolymer (B)>

The solution obtained by dissolving the rigid copolymer (B) in tetrahydrofuran was used as a measurement sample, and the measurement was performed using a GPC device (manufactured by Tosoh Co., Ltd.), and it was calculated using a standard polystyrene conversion algorithm.

<Synthesis example 1: Rubber polymer (S-1)>

Add 150 parts of water, 3.3 parts of potassium tallow fatty acid salt, 0.14 parts of potassium hydroxide, 0.3 parts of sodium pyrophosphate, 0.20 parts of tertiary dodecyl mercaptan in the reactor, and then add 100 parts of 1,3-butadiene The temperature was raised to 62°C. Then, 0.12 parts of potassium persulfate was pressed in to start polymerization. The reaction system took 10 hours to reach 75°C and proceeded. Furthermore, after reacting at 75 degreeC for 1 hour, 0.08 part of sodium formaldehyde sulfoxylate was press-injected. After removing the remaining 1,3-butadiene, the polymer was taken out to obtain a latex of rubbery polymer (S-1). The mass average particle diameter of the obtained rubbery polymer (S-1) was 0.08 μm.

<Synthesis example 2: Rubber polymer (G-1)>

Add 0.15 parts of latex of rubber polymer (S-1) and 0.15 parts of sodium dodecylbenzene sulfonate in 100 parts of solid content conversion to the reactor, and adjust the solid content to 36.5% by adding water. After the temperature was raised to 30°C, 0.5 part of acetic acid was added, followed by stirring for 10 minutes, and neutralization with potassium hydroxide to obtain a latex of a rubber polymer (G-1). The mass average particle diameter of the obtained rubbery polymer (G-1) was 0.15 μm.

<Synthesis example 3: Rubber polymer (G-2)>

Add 0.15 parts of latex of rubber polymer (S-1) and 0.15 parts of sodium dodecylbenzene sulfonate in 100 parts of solid content conversion to the reactor, and adjust the solid content to 36.5% by adding water. After the temperature was raised to 30°C, 1.0 part of acetic acid was added, followed by stirring for 10 minutes, and neutralization with potassium hydroxide to obtain a latex of a rubber polymer (G-2). The mass average particle diameter of the obtained rubbery polymer (G-2) was 0.18 μm.

<Synthesis Example 4: Rubber Polymer (G-3)>

Add 0.15 parts of latex of rubber polymer (S-1) and 0.15 parts of sodium dodecylbenzene sulfonate in 100 parts of solid content conversion to the reactor, and adjust the solid content to 36.5% by adding water. After the temperature was raised to 30°C, 1.3 parts of acetic acid was added, followed by stirring for 10 minutes, and neutralization with potassium hydroxide to obtain a latex of a rubber polymer (G-3). The mass average particle diameter of the obtained rubbery polymer (G-3) was 0.20 μm.

<Synthesis Example 5: Rubber Polymer (G-4)>

Add 0.15 parts of latex of rubber polymer (S-1) and 0.15 parts of sodium dodecylbenzene sulfonate in 100 parts of solid content conversion to the reactor, and adjust the solid content to 36.5% by adding water. After the temperature was raised to 30°C, 1.6 parts of acetic acid was added, followed by stirring for 10 minutes, and neutralization with potassium hydroxide to obtain a latex of a rubber polymer (G-4). The mass average particle diameter of the obtained rubbery polymer (G-4) was 0.22 μm.

<Synthesis Example 6: Rubber polymer (g-5)>

Add 100 parts of rubber polymer (S-1) latex and 0.15 parts of sodium dodecylbenzene sulfonate to the reactor in terms of solid content, and adjust the solid content to 36.5% by adding water. After the temperature was raised to 30°C, 0.4 part of acetic acid was added, followed by stirring for 10 minutes, and neutralization with potassium hydroxide to obtain a latex of a rubber polymer (g-5). The mass average particle diameter of the obtained rubbery polymer (g-5) was 0.14 μm.

<Synthesis Example 7: Rubber Polymer (S-2)>

Add 120 parts of water, 1.4 parts of potassium rosinate, 0.6 parts of potassium tallow fatty acid salt, 0.001 parts of sodium hydroxide, 0.2 parts of sodium sulfate, 1.4 parts of styrene, and 0.15 parts of tertiary dodecyl mercaptan in the reactor. After nitrogen replacement, 26.2 parts of 1,3-butadiene and 0.1 part of dicumyl hydroperoxide were added, and the temperature was raised to 50°C. Then, an aqueous solution obtained by dissolving 0.002 parts of iron sulfate heptahydrate, 0.09 parts of sodium pyrophosphate, and 0.34 parts of sodium formaldehyde sulfoxylate in 6.4 parts of water was press-fitted to start polymerization, and the temperature was raised to 56°C over 30 minutes. In the reaction system, 68.8 parts of 1,3-butadiene, 3.6 parts of styrene, 1.5 parts of dicumyl hydroperoxide, and 0.28 parts of tertiary dodecyl mercaptan were added successively while reacting for 7 hours, which lasted for 1 hour. It is carried out at 65°C. Furthermore, after reacting at 65°C for 1 hour, the remaining 1,3-butadiene was removed, and the polymer was taken out to obtain a latex of a rubbery polymer (S-2). The mass average particle diameter of the obtained rubbery polymer (S-2) was 0.09 μm.

<Synthesis Example 8: Graft Copolymer Containing Rubber (A-I-1)>

Add 40 parts of rubber polymer (G-1) latex, 85 parts of water, 0.3 parts of potassium rosinate, and 0.42 parts of fructose to the reactor in terms of solid content converted to 40 parts, and then add 0.008 parts of iron sulfate heptahydrate , After dissolving 0.21 part of sodium pyrophosphate in 5 parts of water, the temperature is raised to 60°C. In the reaction system, 44.4 parts of styrene, 15.6 parts of acrylonitrile, 0.42 parts of cumene hydroperoxide, and 0.24 parts of tertiary dodecyl mercaptan were added successively, and the temperature was increased from the starting temperature of 60°C for 150 minutes after heating. It was carried out at 73°C to obtain the latex of the rubber-containing graft copolymer (AI-1). The rubber-containing graft copolymer (A-I-1) latex is a powdered rubber-containing graft copolymer that undergoes a well-known coagulation and drying step. Table 1 shows the mass average particle size and particle size distribution of the rubber polymer in the rubber-containing graft copolymer (A-I-1).

<Synthesis Example 9: Rubber-containing graft copolymer (A-I-2)>

Except changing the latex of the rubbery polymer (G-1) to the latex of the rubbery polymer (G-2), polymerization was carried out in the same manner as in Synthesis Example 8 to obtain a rubber-containing graft copolymer ( AI-2). Table 1 shows the mass average particle size and particle size distribution of the rubbery polymer in the obtained rubber-containing graft copolymer (A-I-2).

<Synthesis Example 10: Graft Copolymer Containing Rubber (A-I-3)>

Except that the latex of the rubber polymer (G-1) was changed to the latex of the rubber polymer (G-3), polymerization was carried out in the same manner as in Synthesis Example 8 to obtain a rubber-containing graft copolymer ( AI-3). Table 1 shows the mass average particle size and particle size distribution of the rubbery polymer in the obtained rubber-containing graft copolymer (A-I-3).

<Synthesis Example 11: Rubber-containing graft copolymer (A-I-4)>

Except changing the latex of the rubbery polymer (G-1) to the latex of the rubbery polymer (G-4), polymerization was carried out in the same manner as in Synthesis Example 8 to obtain a rubber-containing graft copolymer ( AI-4). Table 1 shows the mass average particle size and particle size distribution of the rubbery polymer in the obtained rubber-containing graft copolymer (A-I-4).

<Synthesis Example 12: Graft Copolymer Containing Rubber (A-I-5)>

Except that the latex of the rubber polymer (G-1) was changed to the rubber polymer (g-5), polymerization was carried out in the same manner as in Synthesis Example 8 to obtain a rubber-containing graft copolymer (AI- 5). Table 1 shows the mass average particle size and particle size distribution of the rubbery polymer in the obtained rubber-containing graft copolymer (A-I-5).

<Synthesis Example 13: Acid group-containing copolymer (K-1)>

Add 200 parts of water, 88 parts of n-butyl acrylate, 12 parts of methacrylic acid, 2 parts of potassium oleate, 1 part of sodium dioctylsulfosuccinate, 0.4 parts of cumene hydroperoxide, and formaldehyde sulfoxylate in the reactor. 0.3 parts of sodium hydrogen, polymerization was carried out at 70°C for 4 hours. The mass average particle diameter of the obtained acid group-containing copolymer (K-1) latex was 0.07 μm, and the pH was 9.1.

<Synthesis Example 14: Acid group-containing copolymer (K-2)>

Except that n-butyl acrylate was changed to 85 parts and methacrylic acid was changed to 15 parts, polymerization was performed in the same manner as in Synthesis Example 13 to obtain an acid group-containing copolymer (K-3) latex. The mass average particle diameter of the obtained acid group-containing copolymer (K-3) latex was 0.121 μm and the pH was 9.2.

<Synthesis Example 15: Acid group-containing copolymer (K-3)>

Except that n-butyl acrylate was changed to 80 parts, methacrylic acid was changed to 20 parts, and potassium oleate was changed to 1.5 parts, polymerization was carried out in the same manner as in Synthesis Example 13 to obtain an acid group-containing copolymer (K-3) Latex. The obtained acid group-containing copolymer (K-3) latex had a mass average particle size of 0.145 μm and a pH of 9.2.

<Synthesis Example 16: Acid group-containing copolymer (K-4)>

Except that n-butyl acrylate was changed to 87 parts, methacrylic acid was changed to 13 parts, and potassium oleate was changed to 2.5 parts, polymerization was carried out in the same manner as in Synthesis Example 13 to obtain an acid group-containing copolymer (K-2) Latex. The obtained acid group-containing copolymer (K-4) latex had a mass average particle size of 0.095 μm and a pH of 9.1.

<Synthesis Example 17: Rubber-containing graft copolymer (A-I-6)>

Add 45 parts of rubber polymer (S-2) latex in terms of solid content to the reactor, and then add 0.8 parts of acid group-containing copolymer (K-1) under stirring. ) After the latex, stir for 40 minutes to obtain a swollen rubber polymer (g-6). Then, 40 parts of water and 0.45 parts of glucose were added, and after raising the temperature to 50°C, 0.006 parts of iron sulfate heptahydrate and 0.12 parts of sodium pyrophosphate were added. The reaction system is carried out by adding 39.0 parts of styrene, 16.0 parts of acrylonitrile, 0.50 parts of tertiary dodecyl mercaptan, and 0.44 parts of cumene hydroperoxide one by one. Latex of graft copolymer (AI-6) containing rubber. The rubber-containing graft copolymer (A-I-6) latex is a powdered rubber-containing graft copolymer through a well-known coagulation and drying step.

The mass average particle size and particle size distribution of the swollen rubber polymer (g-6) of the obtained rubber-containing graft copolymer (A-I-6) are shown in Table 1.

<Synthesis Example 18: Graft Copolymer Containing Rubber (A-II-1)>

Add 60 parts of rubber polymer (S-2) latex in terms of solid content to the reactor, and then add 1.3 parts of acid group-containing copolymer (K-2) under stirring. ) After the latex, stir for 40 minutes to obtain a swollen rubber polymer (G-7). Then, 28 parts of water, 0.45 parts of glucose, 2.8 parts of styrene, 1.2 parts of acrylonitrile, 0.075 parts of tertiary dodecyl mercaptan, and 0.016 parts of cumene hydroperoxide were added. After the temperature was raised to 50°C, sulfuric acid was added. 0.002 parts of iron heptahydrate and 0.05 parts of sodium pyrophosphate.

The reaction system was carried out by successively adding 25.6 parts of styrene, 10.4 parts of acrylonitrile, 0.68 parts of tertiary dodecyl mercaptan, and 0.14 parts of cumene hydroperoxide, and proceeding from the initial temperature of 50°C to 65°C to obtain Latex of graft copolymer containing rubber (A-II-1). The rubber-containing graft copolymer (A-II-1) latex is a powdered rubber-containing graft copolymer that undergoes a well-known coagulation and drying step. Table 1 shows the mass average particle size and particle size distribution of the swollen rubber polymer (G-7) in the obtained rubber-containing graft copolymer (A-II-1).

<Synthesis Example 19: Graft Copolymer Containing Rubber (A-II-2)>

Except for changing to the acid group-containing copolymer (K-3) latex, polymerization was carried out in the same manner as in Synthesis Example 17 to obtain a rubber-containing graft copolymer (A-II-2) latex. Table 1 shows the mass average particle size and particle size distribution of the bulged rubber polymer (G-8) of the obtained rubber-containing graft copolymer (A-II-2).

<Synthesis Example 20: Rubber Polymer (g-9)>

Add 100 parts of rubber polymer (S-2) latex converted to solid content into the reactor, and then add 1.3 parts of acid group-containing copolymer (K-3 converted to solid content) under stirring. ) After the latex, stir for 40 minutes to obtain a swollen rubber polymer (g-9). The mass average particle diameter of the obtained rubbery polymer (g-9) was 0.44 μm.

<Synthesis Example 21: Rubber polymer (g-10)>

Add 100 parts of rubber polymer (S-2) latex in terms of solid content to the reactor, and then add 1.3 parts of acid group-containing copolymer (K-4 ) After the latex, stir for 40 minutes to obtain a swollen rubber polymer (g-10). The mass average particle diameter of the obtained rubbery polymer (g-10) was 0.28 μm.

<Synthesis Example 22: Graft Copolymer Containing Rubber (A-II-3)>

Add 9 parts by mass of swollen rubber polymer (g-9) in terms of solid content, and 36 parts by mass of swollen rubber polymer (g-10) in terms of solid content into the reactor. 85 parts of water, 0.3 parts of potassium rosinate, 0.42 parts of fructose, and then an aqueous solution of 0.008 parts of iron sulfate heptahydrate and 0.21 part of sodium pyrophosphate dissolved in 5 parts of water was added, and the temperature was raised to 60°C. In the reaction system, 39 parts of styrene, 16 parts of acrylonitrile, 0.42 parts of cumene hydroperoxide, 0.24 parts of tertiary dodecyl mercaptan are added successively, and the temperature is increased from the starting temperature of 60°C for 150 minutes after heating to achieve It was carried out at 73°C to obtain the latex of the rubber-containing graft copolymer (A-II-3). The rubber-containing graft copolymer (A-II-3) latex is a powdered rubber-containing graft copolymer through a well-known coagulation and drying step. Table 1 shows the mass average particle size and particle size distribution of the rubbery polymers (g-9) and (g-10) in the obtained rubber-containing graft copolymer (A-II-3).

<Synthesis Example 23: Rigid Copolymer (B-1)>

In the reactor, add 125 parts of water, 0.4 parts of calcium phosphate, 0.003 parts of potassium alkenyl succinate, 0.05 parts of 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 1,1 -0.04 parts of bis(tertiary hexyl peroxy) cyclohexane, 0.04 parts of tert-butyl peroxy-2-ethylhexyl carbonate, 0.38 parts of tertiary dodecyl mercaptan, and 72 parts of styrene, A monomer mixture composed of 28 parts of acrylonitrile and reacted. The reaction system was carried out while gradually adding water, acrylonitrile, and a part of styrene, and heating from the starting temperature of 65°C for 6.5 hours to reach 125°C. Furthermore, after reacting at 125°C for 1 hour, a hard copolymer (B-1) slurry was obtained. After cooling, the slurry was subjected to centrifugal dehydration to obtain a rigid copolymer (B-1). The mass average molecular weight of the obtained rigid copolymer was 121,000, and the content of monomer units derived from the vinyl cyanide compound was 27.2% by mass.

<Synthesis Example 24: Rigid Copolymer (B-2)>

Except that the amount of styrene was changed to 75 parts, the amount of acrylonitrile was changed to 25 parts, and the amount of tertiary dodecyl mercaptan was changed to 0.55 parts, the same procedure as in Synthesis Example 23 was carried out except that Polymerize to obtain a rigid copolymer (B-2). The mass average molecular weight of the obtained rigid copolymer (B-2) was 79,000, and the content of monomer units derived from the vinyl cyanide compound was 24.4% by mass.

<Synthesis Example 25: Rigid Copolymer (B-I-1)>

Except that the amount of styrene was changed to 66 parts, the amount of acrylonitrile was changed to 34 parts, and the amount of tertiary dodecyl mercaptan was changed to 0.51 part, the same procedure as in Synthesis Example 23 was performed except that Polymerize to obtain a rigid copolymer (BI-1). The mass average molecular weight of the obtained rigid copolymer (B-I-1) was 71,000, and the content of monomer units derived from the vinyl cyanide compound was 32.3% by mass.

<Synthesis Example 26: Rigid Copolymer (B-I-2)>

Except that the amount of styrene was changed to 68 parts, the amount of acrylonitrile was changed to 32 parts, and the amount of tertiary dodecyl mercaptan was changed to 0.88 parts, it was performed in the same manner as in Synthesis Example 23. Polymerize to obtain a rigid copolymer (BI-2). The mass average molecular weight of the obtained rigid copolymer was 53,000, and the content of monomer units derived from the vinyl cyanide compound was 30.2% by mass.

<Synthesis Example 27: Rigid Copolymer (B-I-3)>

Except that the amount of styrene was changed to 62 parts, the amount of acrylonitrile was changed to 38 parts, and the amount of tertiary dodecyl mercaptan was changed to 0.87 parts, the same procedure as in Synthesis Example 23 was carried out except that Polymerize to obtain a rigid copolymer (BI-3). The mass average molecular weight of the obtained rigid copolymer was 52,000, and the content of monomer units derived from the vinyl cyanide compound was 34.8% by mass.

<Synthesis Example 28: Rigid Copolymer (B-I-4)>

Except that the amount of tertiary dodecyl mercaptan was changed to 0.58 parts, polymerization was carried out in the same manner as in Synthesis Example 26 to obtain a rigid copolymer (B-I-4). The mass average molecular weight of the obtained rigid copolymer was 78,000, and the content of monomer units derived from the vinyl cyanide compound was 30.1% by mass.

<Synthesis Example 29: Rigid Copolymer (B-I-5)>

Except that the amount of tertiary dodecyl mercaptan was changed to 0.55 parts, polymerization was carried out in the same manner as in Synthesis Example 27 to obtain a rigid copolymer (B-I-5). The mass average molecular weight of the obtained rigid copolymer was 79,000. The content of the monomer unit derived from the vinyl cyanide compound was 34.7% by mass.

<Example 1 to Example 16, Comparative Example 1 to Comparative Example 8>

(Manufacturing of thermoplastic resin composition)

According to the ratio shown in Table 2 to Table 4, the rubber-containing graft copolymer (A-I, A-II) and the rigid copolymer (B) were mixed to prepare a thermoplastic resin composition for plating.

Using a 30mm twin-screw extruder ("TEX30α" manufactured by Nippon Steel Co., Ltd.), the obtained thermoplastic resin composition for plating was melted and kneaded at a temperature of 200°C, and pelletized to obtain the thermoplastic resin composition for plating. Particles of resin composition.

The following evaluations were performed on the thermoplastic resin composition for plating of each example. The results are shown in Table 2 to Table 4.

(Evaluation of plating adhesion strength)

Using a 75-ton injection molding machine ((stock) "JSW-75EIIP" manufactured by Nippon Steel Co., Ltd., pellets of the thermoplastic resin composition were injection-molded to obtain test pieces. The injection molding system uses a mold for evaluation of plating adhesion strength (length 90mm) ×width 50mm×thickness 3mm), the cylinder temperature is 250°C, the mold temperature is 60°C, and the injection speed is any of 3 levels of low speed (1mm/sec), medium speed (3mm/sec), and high speed (10mm/sec) Under the conditions of the person.

The obtained test piece was subjected to plating processing, and the plating film was peeled off in the vertical direction on a load measuring device, the peel strength was measured, and the plating adhesion strength was determined according to the following criteria.

A: The plating adhesion strength exceeds 15 N/cm, which is very excellent.

B: The plating adhesion strength is 9.8 N/cm or more and less than 12 N/cm, and there is no practical problem.

C: The plating adhesion strength is 9.8 N/ or less, which does not reach the practical level.

In the evaluation of the plating adhesion strength, the plating process was implemented in the following order (1) to (15).

(1) Degreasing step [50℃×5 minutes]

Soak for 5 minutes in an alkaline degreasing solution heated at 50°C.

(2) Washing

It was immersed in water at 23° C. for 1 minute and washed with water.

(3) Etching treatment (CrO ₃ : 400g/l, sulfuric acid: 200ml/l) [65℃×15 minutes]

The etching solution composed of anhydrous chromic acid: 400g/l and 98% sulfuric acid: 200ml/l is heated to 65°C and immersed for 10 minutes.

(4) Washing

It was immersed in water at 23° C. for 1 minute and washed with water.

(5) Acid treatment [23℃×1min]

Immerse in an acid treatment solution consisting of 35% hydrochloric acid: 100ml/l at 23°C for 1 minute.

(6) Washing

It was immersed in water at 23° C. for 1 minute and washed with water.

(7) Catalytic treatment [30℃×3 minutes]

The tin-palladium mixed catalyst solution, which is usually called a catalyst, is heated to 30°C and immersed for 3 minutes.

(8) Washing

It was immersed in water at 23° C. for 1 minute and washed with water.

(9) Activation treatment [40℃×3 minutes]

The activation solution consisting of 98% sulfuric acid: 100ml/l is heated to 40°C and immersed for 3 minutes.

(10) Washing

It was immersed in water at 23° C. for 1 minute and washed with water.

(11) Electroless nickel plating treatment [40℃×5 minutes]

The electroless nickel plating solution with hypophosphite as the reducing agent is heated to 40°C and immersed for 5 minutes.

(12)Washing

It was immersed in water at 23° C. for 1 minute and washed with water.

(13) Copper electroplating treatment [Film thickness: 35μm 20℃×60 minutes]

The copper electroplating solution containing copper sulfate, sulfuric acid, and brightener was set to 20° C., and plating was performed for 60 minutes to obtain a copper plating film thickness of 35 μm.

(14)Washing

It was immersed in water at 23° C. for 1 minute and washed with water.

(15) Drying [80℃×2 hours]

Using a hot air dryer set at 80°C, the obtained plated processed product was dried for 2 hours.

(Evaluation of cooling and heating cycle characteristics)

Using a 75-ton injection molding machine ((stock) "JSW-75EIIP" manufactured by Nippon Steel Co., Ltd., the pellets of the thermoplastic resin composition were injection-molded to obtain test pieces. The injection molding system used a mold for thermal cycle evaluation (length 100mm×width) 100mm×thickness 3mm), under the conditions of a cylinder temperature of 200°C, a mold temperature of 60°C, and an injection speed of 30mm/sec.

A plating process was performed on the obtained test piece, and [-40 degreeC x 1 hour cooling and 80 degreeC x 1 hour heating] were set to 1 cycle and 8 cycles were performed. Then, the state of the plated film of the product was visually observed, and the cooling and heating cycle characteristics were judged according to the following criteria.

A: There is no change in the plating film, which is very excellent.

B: There is some swelling in the plating film, but there is no problem in practical use.

C: There are changes such as swelling in the plating film, which does not reach the practical level.

In the evaluation of the thermal cycle characteristics, the plating process was carried out in the following order (1) to (17).

(1) Degreasing step [50℃×5 minutes]

Soak for 5 minutes in an alkaline degreasing solution heated at 50°C.

(2) Washing

It was immersed in water at 23° C. for 1 minute and washed with water.

(3) Etching treatment (CrO ₃ : 400g/l, sulfuric acid: 200ml/l) [65℃×20 minutes]

The etching solution composed of anhydrous chromic acid: 400g/l and 98% sulfuric acid: 200ml/l is heated to 65°C and immersed for 20 minutes.

(4) Washing

It was immersed in water at 23° C. for 1 minute and washed with water.

(5) Acid treatment [23℃×1min]

Immerse in an acid treatment solution consisting of 35% hydrochloric acid: 100ml/l at 23°C for 1 minute.

(6) Washing

It was immersed in water at 23° C. for 1 minute and washed with water.

(7) Catalytic treatment [30℃×3 minutes]

The tin-palladium mixed catalyst solution, which is usually called a catalyst, is heated to 30°C and immersed for 3 minutes.

(8) Washing

It was immersed in water at 23° C. for 1 minute and washed with water.

(9) Activation treatment [40℃×3 minutes]

The activation solution consisting of 98% sulfuric acid: 100ml/l is heated to 40°C and immersed for 3 minutes.

(10) Washing

It was immersed in water at 23° C. for 1 minute and washed with water.

(11) Electroless nickel plating treatment [40℃×5 minutes]

The electroless nickel plating solution with hypophosphite as the reducing agent is heated to 40°C and immersed for 5 minutes.

(12)Washing

It was immersed in water at 23° C. for 1 minute and washed with water.

(13) Copper electroplating treatment [Film thickness: 20μm 20℃×20 minutes]

The copper electroplating solution containing copper sulfate, sulfuric acid, and brightener was set to 20° C., and plating was performed for 20 minutes to obtain a copper plating film thickness of 20 μm.

(14)Washing

It was immersed in water at 23° C. for 1 minute and washed with water.

(15) Nickel plating treatment [Film thickness: 10μm 55℃×15 minutes]

The nickel electroplating solution containing nickel sulfate, nickel chloride, and brightener was set to 55° C., and plating was performed for 15 minutes to obtain a nickel plating film thickness of 15 μm.

(16)Washing

It was immersed in water at 23° C. for 1 minute and washed with water.

(17) Chrome plating treatment [Film thickness: 0.3μm 45℃×2 minutes]

The chromium electroplating solution containing anhydrous chromic acid and sulfuric acid was set to 45° C., and plating was performed for 2 minutes to obtain a chromium plating film thickness of 0.3 μm.

(Evaluation of Charpy impact strength)

Using a 75-ton injection molding machine ("J75EII-P" manufactured by Nippon Steel Co., Ltd.), pellets of the thermoplastic resin composition were injection molded to obtain test pieces (length 80mm, width 10mm, thickness 4mm). Injection molding is performed under the conditions of a molding temperature of 235°C and a mold temperature of 60°C.

For the obtained test piece, the Charpy impact strength (with a notch) was measured at a measurement temperature of 23° C. in accordance with ISO (International Organization for Standardization) 179, and the impact resistance was judged according to the following criteria.

A: The Charpy impact strength is 20 kJ/m ² or more, which is very excellent.

B: The Charpy impact strength is 16 kJ/m ² or more and less than 20 kJ/m ² and there is no practical problem.

C: The Charpy impact strength did not reach 16 kJ/m ² and did not reach a practical level.

(Evaluation of fluidity (spiral flow))

Using a spiral flow mold (width 15mm×thickness 2mm), under the conditions of a cylinder temperature of 270°C, a mold temperature of 60°C, and an injection pressure of 100MPa, the pellets of the thermoplastic resin composition were ejected from an 85-ton injection molding machine ((stock) Nippon Steel Co., Ltd.) The manufactured "J85AD-110H" is injection molded. The spiral flow length (mm) of the molded product obtained is measured, and the fluidity (spiral flow) is judged according to the following criteria.

A: The spiral flow length is 450 mm or more and the material properties are excellent.

B: The spiral flow length is 380 mm or more and less than 450 mm, and there is no practical problem.

C: The spiral flow length does not reach 380 mm and does not reach a practical level.

(Comprehensive judgment)

In the above evaluation results, a thermoplastic resin composition with all evaluations of "A" in plating adhesion strength, thermal cycle characteristics, Charpy impact strength, and fluidity (spiral flow) was judged as "S" in the comprehensive judgment. In addition, all the thermoplastic resin compositions evaluated as "A" or "B" and having three or more "A"s were judged as "A" in the comprehensive judgment. In addition, all the thermoplastic resin compositions evaluated as "A" or "B" and "A" is 2 or less are judged as "B" in the comprehensive judgment. The thermoplastic resin composition judged as "C" in at least one item is judged as "C" in the comprehensive judgement.

It can be seen that the thermoplastic resin compositions of Examples 1 to 16 provide resin molded products with excellent adhesion strength characteristics, thermal cycle characteristics, impact resistance, and fluidity in the plating step.

Since the thermoplastic resin composition of Comparative Example 1 only uses one rubber-containing graft copolymer (A-I) as the rubber-containing graft copolymer, it has poor thermal cycle characteristics and impact resistance.

In the thermoplastic resin composition of Comparative Example 2, since the content of the rubber-containing graft copolymer (A-I) in the rubber-containing graft copolymer mixture (A) is less than 60% by mass, the adhesive strength characteristics during high-speed molding are poor.

In the thermoplastic resin composition of Comparative Example 3, since the content of the rubber-containing graft copolymer (A-I) in the rubber-containing graft copolymer mixture (A) is 95% by mass or more, the thermal cycle characteristics are poor.

Since the thermoplastic resin composition of Comparative Example 4 used only one rubber-containing graft copolymer (A-II) as the rubber-containing graft copolymer, the adhesive strength characteristics during medium-speed molding and high-speed molding were poor.

The thermoplastic resin composition of Comparative Example 5 has poor impact resistance because the mass average particle diameter of the rubbery polymer of the rubber-containing graft copolymer (A-I) is less than 0.15 μm.

In the thermoplastic resin composition of Comparative Example 6, since the particle diameter of the rubber-containing graft copolymer (AI) exceeds 0.122 μm and is less than 0.243 μm, the proportion of particles of all rubber polymer particles is less than 50% by mass. , So the adhesion strength characteristics during high-speed forming are poor.

Since the thermoplastic resin composition of Comparative Example 7 is composed of the rubber-containing graft copolymer (A-I), the rubber-containing graft copolymer mixture has poor thermal cycle characteristics.

The thermoplastic resin composition of Comparative Example 8 only uses a rubber-containing graft copolymer (A-II-3) obtained by copolymerizing a monomer mixture in the presence of two rubbery polymers with different mass average particle diameters. As a rubber-containing graft copolymer, it has poor adhesion strength characteristics during medium-speed molding and high-speed molding.

(Industrial availability)

According to the present invention, it is possible to provide a thermoplastic resin composition for plating, a resin molded product formed by molding the thermoplastic resin composition, and a plated processed product. The thermoplastic resin composition for plating can provide a plating step A resin molded product with excellent adhesion strength characteristics, thermal cycle characteristics, impact resistance, and fluidity. Therefore, the present invention is extremely important in industry.

Claims (4)

A thermoplastic resin composition for plating, comprising a rubber-containing graft copolymer mixture (A) and a rigid copolymer (B). The rubber-containing graft copolymer mixture (A) is composed of two or more rubber-containing It is composed of a graft copolymer, and the aforementioned rubber-containing graft copolymer is formed by copolymerizing a monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a diene-based rubber polymer. The rigid copolymer (B) has a monomer unit derived from an aromatic vinyl compound and a monomer unit derived from a vinyl cyanide compound; the aforementioned rubber-containing graft copolymer mixture (A) includes: a rubber-containing graft The copolymer (AI) and the rubber-containing graft copolymer (A-II), wherein the diene rubber polymer in the rubber-containing graft copolymer (AI) has a mass average particle diameter of 0.15 μm or more and The proportion of particles with a particle size of less than 0.25 μm and a particle size of more than 0.122 μm and less than 0.243 μm in the total particles of the diene rubber polymer is 50% by mass or more. The rubber-containing graft copolymer (A -II) The mass average particle diameter of the aforementioned diene rubber polymer is 0.25 μm or more and 0.5 μm or less; the content of the aforementioned rubber-containing graft copolymer (AI) is relative to the aforementioned rubber-containing graft copolymer mixture The total mass of (A) is 60% by mass or more and less than 95% by mass; when the total mass of the aforementioned rubber-containing graft copolymer mixture (A) and the aforementioned rigid copolymer (B) is 100 parts by mass, the aforementioned The content of the rubber-containing graft copolymer mixture (A) is 25 parts by mass or more and 50 parts by mass or less, and the content of the aforementioned rigid copolymer (B) is 50 parts by mass or more and 75 parts by mass or less. The thermoplastic resin composition for plating as described in claim 1, wherein the rigid copolymer (B) comprises a rigid copolymer (BI), and the mass average molecular weight of the rigid copolymer (BI) is 50,000 or more and 80,000 or less, and the source The content of the monomer unit of the self-cyanated vinyl compound is 30% by mass or more and 35% by mass or less with respect to the total mass of the aforementioned rigid copolymer. A resin molded product composed of the thermoplastic resin composition for plating as described in claim 1 or 2. A plated processed product having a resin molded product and a plated film. The resin molded product is the resin molded product described in claim 3, and the plated film is formed on at least a part of the surface of the resin molded product.